Color formers containing a m-alkyl-phenoxyacyl group



United States Patent 3,285,747- COLOR FORMERS CONTAINING A m-ALKYL- PHENOXYACYL GROUP Robert F. Coles, North St. Paul, Minn., assignor to General Analiue & Film Corporation, New York, N.Y., a corporation of Delaware No Drawing. Filed Aug. 26, 1964, Ser. No. 392,330 3 Claims. (Cl. 96100) This application is a continuation-impart of application Serial No. 681,884,- filed September 4, 1957, now abandoned.

This invention relates to color photography and particularly to color-forming coupler compounds containing a m-alkylphenoxyacylgroup.

' It is known that a colored image may beproduced by adding to certain developer solutions or by incorporating in the gelatino silver-halide emulsion, a compound which couples during development with the oxidation products of the developing agent to form a colored substance which is deposited close to the silver grains of the silver image during development. Such a compound, which is employed in conjunction with a developing agent for the exposed silver-halide and which couples with the oxidation product of said developing agent during development, is referred to herein .as a coupling component or coupler.

In order to be of use in color photography, a coupler must produce. a dye image of suitable stability and spectral' characteristics. In addition to the above properties, a coupler must be capable of being incorporated in a photographic emulsion. and be fast to diffusion. Thus, couplers may be incorporated. in a photographic emulsion by dispersing therein a solution of said coupler in an oily water-immiscible solvent such as tricresyl phosphate, dibutyl phthalate, and. the like. Alternately, couplers may be employed that are alkali soluble and, therefore, can be dissolved directly in the photographic emulsion. In order to render the couplers fast to. diffusion in the gelatino silver-halide emulsion, it is usual to introduce into the coupler molecule a. molecule enlarging group such as a long alkyl chain. Although the prior art contains numerous patents on color formers, very few of them possess the aforementioned properties which render them suitable for use in color photography.

It is, therefore, an object of this invention to provide a coupler characterized by improved fastness to diffusion in a photographic emulsion.

Another object is to provide a coupler having extremely high solubility in water-immiscible organic solvents.

A still further object of this invention is to provide color-forming components possessing relatively low meltingrpoints.

A still further object is to provide photographic emulsions containing color formers, characterized by extremely high solubility in water-immiscible organic solvents and low melting points.

Other objects and advantages of this invention will be apparent as the description proceeds.

The above objects are realized by incorporating into one of the usual color coupler molecules, i.e., a ketomethylene compound, a pyrazolone or a. phenol, am-alkylphenoxyacyl residue in which the alkyl radical contains at least carbon atoms. Thisgroup maybe readily introduced by conventional methods into color-forming moieties that contain a primary or secondary amino group, a reactive hydroxyl group or other suitable linkages. The coupling components thus obtained. are extremely soluble in water-immiscible organic solvents such as tricresyl phosphate, dibutyl phthalate, and the like and possess low melting points, generally 100 C. or lower. This property is highly desirable in a dispersed droplet type of color former and dye system, since it produces a system which hasonly a slight tendency toward crystallization. In fact, the aforesaid properties of highsolubility in organic solvents and low melting point make these couplers particularly suitable in mixed-grain type emulsions.

The color couplers contemplated herein can be represented by the following general formulae :1

wherein R is hydrogen, an alkyl group, i.e., methyl, ethyl, n-propyl, n-butyl, sec.-butyl, amyl", iso-amyl', hexyl, heptyl, etc.; R is a long chain alkyl group containing from 10 to 20 carbon: atoms, i.e., capryl, undecylyl, lauryl, myristyl, pentadecyl, palmityl, stearyl, etc; R 1 is a methyl group; R is hydrogen or an alkyl group as given above for R; A represents that part of the molecule that contains the coupling function such as. a reactive methylene or phenolic hydroxyl group capable of coupling with the oxidation products. of a primary aromatic amino color developing agent, and Y is Specific compounds which maybe used according to. this invention are the following:

N-(1hydroxy-2-n aph'thoy1)-N.'-[or(3-pentadecylphenoxy)- n=butyryl1 -'1,6 hexanediamine N (4-chloro-1-hydr0xy-2-naphthoyl N'- ['a- 3-pentadecy1- phenoxy) -n.-butry1]-1,6-hexanedia1nine This invention is further illustrated by the following examples but it is to be understood that the invention is not to be restrictedthereto.

PREPARATION OF INTERMEDIATES Example IL-a-( m-pentadecylphenoxy.)-nrbutyric acid In a 3-liter triple-necked flask, equippedawith a reflux condenser, stirrer and dropping funnel was placed a solution of m-pentadecylphenol (608 g., 2.0 moles) in 1300 ml; of ethanol containing 16.0 g. (4.0.moles) ofso dium hydroxide. The solution was cooled slightly in water and a-bromobutyric acid (334 g., 2.0 moles) was added at a rate sufiicient to cause a gentle reflux. The mixture was heated at reflux for 3 hours and then an additional 20 g. of sodium hydroxide and 42 g. of a-bromobutyric acid were added and heating continued for 3 hours. A second and third addition was made in the same manner. The solution was then poured into 4- liters of ice Water and acidified strongly with hydrochloric acid. After collecting the precipitated product and washing with water, the material was Washed with cold methanol and then recrystallized from 2-liters of methanol. Yield 600 g., M.P. 81-84 C.

The acid chloride of the above compound was prepared by allowing a mixture of carboxylic acid (200 g.) and thionyl chloride (300 ml.) to stand for 24 hours. The resulting solution was degassed and most of the excess thionyl chloride was removed on an aspirator. Finally, the remaining thionyl chloride was removed at below 40 C. under vacuum pump pressure. The residual oil was used without purification.

PREPARATION OF COLOR FORMERS Example II.4,6-dichlr0-2-[a-(3'-pentadecylphenoxy)- n-butyramido] -phen0l To a solution of 2-amino-4,6-dichlorophenol (26.7 g., 0.15 mole) in dry benzene (350 ml.) was added potassium acetate (15 g., 0.15 mole). After cooling to 10 C., the acid chloride prepared in Example I (61.5 g., 0.15 mole) was added dropwise with stirring. The reaction mixture was stirred cold for 3 hours and then on a steam bath for 1 hour. Decolorizing carbon was added and the mixture filtered. The benzene was removed on a steam bath at reduced pressure and the residue was treated with ice and water. The resulting solid was stirred with dilute sodium bicarbonate solution in a Waring Blendor, filtered and dried. The product may be used in this form or further purified by crystallization from low boiling petroleum ether (M.P. 57-59.5 C.)

Example III .-N (1 -hydr0xy-2-naphthoyl -N [a- (3- pentadecylphenoxy -n-batyryl] -1,6-hexanediamine The amine of the following constitution:

was prepared by reacting phenyl l-hydroxy-Z-naphthoate and a 4 mole excess of examethylenediamine in cold benzene.

A solution of the resulting amine (14.3 g., 0.05 mole) in dry benzene (100 ml.) was cooled in ice and the acid chloride of Example I (20.5 g., 0.05 mole) was added dropwise with stirring. Triethylarnine (29 ml., 0.25 mole) was added dropwise. The reaction mixture was stirred cold for 2 hours and then heated for 2 hours. After filtering, the solvents were removed at reduced pressure and the residue diluted with 100 ml. of petroleum ether; B.P. 30-60 C. The solution was cooled in ice, and the solid collected and crystallized from ethanol. Yield 22 g., M.P. 9294 C.

Example IV. N-(4-chloro-1 -hydroxy-2-naphthoyl)-N (oz (3-pentadecylphen0xy) n batyryl]-1,6-hexanediamine This product was prepared in a manner similar to Example III; 78-79 C. from ethanol. Example V.1-(2,4,6'-trichl0rophenyl)-3-[a-(3'-pentadecylphenoxy)-n-butyramid0]-5-pyraz0l0ne A suspension of S-amino-1-(2,4',6-trichlorophenyl)- 5-pyrazolone (8.3 g., 0.03 mole) in 100 ml. of N-methyl- 2-pyrrolidone was treated dropwise while stirring at C. with the acid chloride of Example I (12.2 g., 0.03

Example VI .3- [a- 3 '-pentadecylphen0xy) butyramido] -1-phenyl-5-pyrazol0ne The product was prepared in a manner similar to Example V except that 3-amino-l-phenyl-S-pyrazolone was substituted for 3 amino-l-(2',4',6'-trichlorophenyl)-5- pyrazolone; M.P. 63-64 C.

Example VII.1 (2'-chl0r0phenyl -3- [a- (3 '-pentadecylphenoxy -n-butyramid0] -5-pyraz0l0ne This product was prepared in the same manner as Example V except that 3amino-1-(2'-chlorophenyl)-5- pyrazolone was substituted for the 3-amino-l-(2',4',6- trichlorophenyl)-5-pyrazolone. The product was crystallized from aceonitrile and melted at 84-85 C.

Example VIIl.a-benz0yl-3-[a-(3'-pentadecylphenoxyl)- n-butyramia'o]-acetanilide The amine of the following constitution:

NHQ

was prepared by the reaction of ethyl benzoylacetate and m-nitroaniline in boiling xylene followed by catalytic reduction of the nitro compound with platinum oxide.

A solution of the above amine hydrochloride (4.4 g., 0.015 mole) in dry pyridine (25 ml.) was chilled in ice and treated dropwise with 6.1 g. (0.015 mole) of the acid chloride from Example I. The reaction mixture was allowed to stand several hours at room temperature and then poured into ice and water containing excess hydrochloric acid. The solid was collected and washed with water and cold methanol. The product was crystallized from about 300 ml. of methanol to yield 5.2 g. of a colorless product; M.P. 55-56 C.

Example IX. N-{p-[N'-benzyl-N'-(p-tolyl)sulfamyl] phenyl} a-{p-[a-(3-pentadecylphenoxy)butyramido] benz0yl}acetamide The amine of the following structure:

was prepared by the reaction of ethyl p-nitrobenzoyl acetate and N-benzyl-N'-(p-tolyl)sulfanilamide followed by the catalytic reduction of the nitro group.

The product was prepared as in Example VIII.

The following example illustrates the manner whereby the couplers herein described are incorporated in a gelatin emulsion.

Example X A solution of 1.5 g. of coupler was dissolved in 6.0 g. of a mixture consisting of 50 parts of phenethyl alcohol, 40 parts of tricresyl phosphate and 10 parts of nbutyl phthalate and the resulting solution dispersed in 20 ml. of a 6% gelatin solution containing .05 ml. of lauryl sulfate. Emulsification was effected by high-speed agitation in a small Waring Blendor. The above dispersion of coupler was mixed with 50 g. of a melted silver-halide gelatin emulsion and then coated on a suitable support, set and dried in the usual manner. On exposure and development of this emulsion with a developing solution employing Z-amino-S-diethylaminotoluene as the developing agent and subsequent removal of silver, a colored image was obtained.

Various photographic developing agents can be employed with the couplers of my invention. The primary aromatic amino developing agents are generally suitable including the phenylenediamines and aminophenols. The alkyl phenylenediamines may be substituted in the amino group as well as in the ring. Suitable compounds are 4-aminoaniline, 4-ethylaminoaniline, 2-diethylaminoaniline, 4-dialkylaminoaniline, e.g., 4-dimethylamin0aniline, 4 diethylaminoaniline, 4-[N-(fl-hydroxyethyD-N- ethyl]aminoaniline, 4 amino-N-ethyl-N-(fi-methanesulfonamidoethyl)-2-methylaniline sulfate, and the like. The above developing agents are preferably used in the form of their salts such as the hydrochloride or hydrosulfate as they are more soluble and stable than the free bases. All of these compounds have a primary amino group which enables the oxidation product of the developer to couple with the color compounds to form dye images. After removal of the silver image by bleaching and fixing in a manner well-known to the art, the color image remains in the emulsion.

A suitable developing solution can be prepared as follows:

G. 2-amino-5-diethylaminotoluene 2 Sodium carbonate (anhydrous) 20 Sodium sulfite (anhydrous) 2 Potassium bromide 0.2

Water to make 1 liter.

The exposed silver-halide emulsions containing the color formers are developed in the above solution in the usual manner. 1

It will be understood that the examples and modifications set forth herein are illustrative only and my invention is to be taken as limited only by the scope of the appended claims.

I claim:

1. A silver halide emulsion containing a coupler compound selected from the class consisting of compounds having one of the following general formula:

2. A silver-halide emulsion containing a coupler compound of the following formula:

' ii t C-N(OH2)aNlCO 3. A silver-halide emulsion containing a coupler compound of the following formula:

OH u i i I i -o-N-(oH,)-No-( Jo- References Cited by the Examiner UNITED STATES PATENTS 2,330,291 9/1943 Kirby 96-100 2,367,531 1/1945 Salminen et al. 96-100 2,423,730 7/1947 Salminen et al. 96-100 40 2,772,161 11/1956 Loria et al. 96-100 X 2,808,329 10/1957 Whitmore 96-100 2,829,975 4/1958 Popeck et al. 96-100 X 2,860,974 11/ 1958 Williams 96-100 2,908,573 10/ 1959 Bush et al. 96-100 5 2,920,961 1/ 1960 Bush et al. 96-100 NORMAN G. TORCHIN, Primary Examiner. J. T. BROWN, D. D. PRICE, Assistant Examiners. 

1. A SILVER HALIDE EMULSION CONTAINING A COUPLER COMPOUND SELECTED FROM THE CLASS CONSISTING OF COMPOUNDS HAVING ONE OF THE FOLLOWING GENERAL FORMULA: 